EP0310352A2 - Method for processing of liquid crystal polymers - Google Patents

Method for processing of liquid crystal polymers Download PDF

Info

Publication number
EP0310352A2
EP0310352A2 EP88308981A EP88308981A EP0310352A2 EP 0310352 A2 EP0310352 A2 EP 0310352A2 EP 88308981 A EP88308981 A EP 88308981A EP 88308981 A EP88308981 A EP 88308981A EP 0310352 A2 EP0310352 A2 EP 0310352A2
Authority
EP
European Patent Office
Prior art keywords
liquid crystal
orientation
foils
lamination
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP88308981A
Other languages
German (de)
French (fr)
Other versions
EP0310352A3 (en
Inventor
Nadka Vassileva Avramova
Stoyko Hristov Fakirov
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SU "KLIMENT OHRIDSKI"
Su Kliment Ohridski
Original Assignee
SU "KLIMENT OHRIDSKI"
Su Kliment Ohridski
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SU "KLIMENT OHRIDSKI", Su Kliment Ohridski filed Critical SU "KLIMENT OHRIDSKI"
Publication of EP0310352A2 publication Critical patent/EP0310352A2/en
Publication of EP0310352A3 publication Critical patent/EP0310352A3/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0079—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/04—Time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/12—Pressure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide

Definitions

  • This invention relates to a method for the processing of liquid crystal polymers which preserves the orientation and hence the associated mechanical properties of the polymers and can find application in the polymer processing industry.
  • Liquid crystal melts are orientated during injection-moulding and the resulting molecular orientation in the molten state is frozen after cooling. This orientation reinforces the material, increasing the modulus of elasticity. (See Ultra-High Modulus Polymers, A. Ciferri and I.M. Ward, Eds., Appl. Sci, Publ., London, 1979).
  • the molecular orientation of liquid crystal polymers depends strongly on the thickness of the article, the thinner the article, the higher the degree of orientation of the polymer molecules. This high degree of orientation provides for good mechanical properties such as high modulus of elasticity and tensile strength. However, the modulus of elasticity drops abruptly with the rise in thickness of the article. Thus a two-fold increase in thickness leads to a multiple decrease in the modulus of elasticity since the two parameters have an exponential dependence. (See W.J. Jackson, Jr., and H.F. Kuhfuss, J. Polym. Sci., Polym. Chem. Ed., 14 , 2043 (1986)). Briefly, the rise in thickness of the liquid crystal article leads to a loss of the unique mechanical properties of liquid crystal polymers.
  • An object of the invention is to provide a method for the processing of liquid crystal polymers by which method, the mechanical properties of the polymer are preserved regardless of the thickness of the processed article.
  • liquid crystal polymer bodies wherein liquid crystal polymer foils with a high degree of orientation are subjected to parallel or cross-ply lamination by heating in a vacuum or in an inert medium to an elevated temperature below the melting point of the polymer.
  • the method of this invention is applicable to polymers capable of undergoing exchange trans-reactions in the solid state, i.e. chemical repairs to breaks in the polymer chain since the occurance of physical repair (based on diffusion) is unlikely for such rigid liquid crystal molecules due to their low mobility.
  • an article of the desired thickness can be obtained, preserving a high degree of orientation in the entire volume and hence excellent mechanical properties.
  • Bonding can be realized also by the application of suitable adhesives or other bonding chemicals.
  • the method of the invention preserves the high mechanical parameters of the thin foils with the high orientation of the liquid crystal molecules.
  • the energy consumption of this method is relatively low since heating is carried out below the melting point of the polymer in the case of lamination. In the case where adhesive compositions are applied, the consumption does not differ from presently used methods.
  • the method can be carried out on the existing equipment for lamination and its duration meets the requirements for industrial applications, The following example illustrates this invention.
  • a foil 200 microns thick, is prepared from a liquid crystal copolymer of polyethyleneterephthalate with 60 mole-%-p-hydroxybenzoic acid (Eastman Kodak Co., USA) by extrusion through a flat extension nozzle and immediate cooling down to 0°C (ice-water) in order to obtain a frozen liquid crystal structure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

Liquid crystal polymer foils with a high degree of orientation are subjected to parallel or cross-ply lamination by heating in a vacuum or in an inert medium to an elevated temperature below the melting point of the polymer to produce a thicker liquid crystal polymer article preserving the orientation and associated mechanical properties of the foils.

Description

  • This invention relates to a method for the processing of liquid crystal polymers which preserves the orientation and hence the associated mechanical properties of the polymers and can find application in the polymer processing industry.
  • It is known that some polymers containing long and rigid molecules can form a liquid crystal phase. Liquid crystal melts are orientated during injection-moulding and the resulting molecular orientation in the molten state is frozen after cooling. This orientation reinforces the material, increasing the modulus of elasticity. (See Ultra-High Modulus Polymers, A. Ciferri and I.M. Ward, Eds., Appl. Sci, Publ., London, 1979).
  • The molecular orientation of liquid crystal polymers depends strongly on the thickness of the article, the thinner the article, the higher the degree of orientation of the polymer molecules. This high degree of orientation provides for good mechanical properties such as high modulus of elasticity and tensile strength. However, the modulus of elasticity drops abruptly with the rise in thickness of the article. Thus a two-fold increase in thickness leads to a multiple decrease in the modulus of elasticity since the two parameters have an exponential dependence. (See W.J. Jackson, Jr., and H.F. Kuhfuss, J. Polym. Sci., Polym. Chem. Ed., 14, 2043 (1986)). Briefly, the rise in thickness of the liquid crystal article leads to a loss of the unique mechanical properties of liquid crystal polymers.
  • An object of the invention is to provide a method for the processing of liquid crystal polymers by which method, the mechanical properties of the polymer are preserved regardless of the thickness of the processed article.
  • According to the present invention there is provided a method for the production of liquid crystal polymer bodies wherein liquid crystal polymer foils with a high degree of orientation are subjected to parallel or cross-ply lamination by heating in a vacuum or in an inert medium to an elevated temperature below the melting point of the polymer.
  • The method of this invention is applicable to polymers capable of undergoing exchange trans-reactions in the solid state, i.e. chemical repairs to breaks in the polymer chain since the occurance of physical repair (based on diffusion) is unlikely for such rigid liquid crystal molecules due to their low mobility. As a result of this treatment of the foils, an article of the desired thickness can be obtained, preserving a high degree of orientation in the entire volume and hence excellent mechanical properties.
  • Bonding can be realized also by the application of suitable adhesives or other bonding chemicals.
  • The method of the invention preserves the high mechanical parameters of the thin foils with the high orientation of the liquid crystal molecules. The energy consumption of this method is relatively low since heating is carried out below the melting point of the polymer in the case of lamination. In the case where adhesive compositions are applied, the consumption does not differ from presently used methods. The method can be carried out on the existing equipment for lamination and its duration meets the requirements for industrial applications,
    The following example illustrates this invention.
    • EXAMPLE
  • A foil, 200 microns thick, is prepared from a liquid crystal copolymer of polyethyleneterephthalate with 60 mole-%-p-hydroxybenzoic acid (Eastman Kodak Co., USA) by extrusion through a flat extension nozzle and immediate cooling down to 0°C (ice-water) in order to obtain a frozen liquid crystal structure. A laminate, 1 mm thick, is prepared from these foils by heating to 170-190°C under pressure of about 3 Mpa under a vacuum, with a preliminary "rinsing" with nitrogen being carried out so that no air is present in the residual atmosphere. Lamination is conducted for 10 hours. The laminate thus obtained had a high tensile modulus of 68,000 kg/cm².

Claims (5)

1. A method for the production of liquid crystal polymer bodies wherein liquid crystal polymer foils with a high degree of orientation are subjected to parallel or cross-ply lamination by heating in a vacuum or in an inert medium to an elevated temperature below the melting point of the polymer.
2. A method as claimed in Claim 1 wherein the liquid crystal foils are from 15 to 200 microns thick.
3. A method as claimed in any preceding claim, wherein lamination takes place under a pressure of 0.05 to 5 Mpa.
4. A method as claimed in Claim 3, wherein lamination takes from 3 to 10 hours.
5. A method as claimed in Claim 1 or 2, wherein the lamination is assisted by use of a chemical bonding agent.
EP88308981A 1987-09-29 1988-09-28 Method for processing of liquid crystal polymers Withdrawn EP0310352A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BG81313/87 1987-09-29
BG81313A BG50083A1 (en) 1987-09-29 1987-09-29 Method for preparing of liquid- crystalline polymer lamillats

Publications (2)

Publication Number Publication Date
EP0310352A2 true EP0310352A2 (en) 1989-04-05
EP0310352A3 EP0310352A3 (en) 1989-07-19

Family

ID=3919597

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88308981A Withdrawn EP0310352A3 (en) 1987-09-29 1988-09-28 Method for processing of liquid crystal polymers

Country Status (3)

Country Link
US (1) US4902369A (en)
EP (1) EP0310352A3 (en)
BG (1) BG50083A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0568083A1 (en) * 1992-04-30 1993-11-03 Mazda Motor Corporation Method for molding a liquid crystal resin sheet and molding apparatus thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0328822A (en) * 1989-06-27 1991-02-07 Nippon Oil Co Ltd Compensating plate for liquid crystal display element
DE4013574A1 (en) * 1990-04-27 1991-10-31 Hoechst Ag AREA SHAPED BODY AND METHOD FOR THE PRODUCTION THEREOF
US5238638A (en) * 1990-08-16 1993-08-24 The University Of Akron Process for preparing a self-reinforced thermoplastic composite laminate
US5268225A (en) * 1990-08-16 1993-12-07 The University Of Akron Self reinforced thermoplastic composite laminate
US5260380A (en) * 1992-01-23 1993-11-09 The University Of Akron Self-reinforced composite and process for preparing same
US6544382B2 (en) 1999-11-15 2003-04-08 Pactiv Corporation Apparatus for high-speed heating and cooling of a polymer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072210A1 (en) * 1981-08-06 1983-02-16 Celanese Corporation Multiaxially oriented high performance laminates comprising uniaxially oriented sheets of thermotropic liquid crystal polymers
EP0133552A1 (en) * 1983-08-13 1985-02-27 BASF Aktiengesellschaft Process for producing a sheet semi-product
EP0201029A2 (en) * 1985-05-08 1986-11-12 Bayer Ag Manufacturing method of articles and sheets of thermotropic polymers
JPS6255130A (en) * 1985-09-05 1987-03-10 三井東圧化学株式会社 Laminated molded shape
JPS6295213A (en) * 1985-10-23 1987-05-01 Asahi Chem Ind Co Ltd Laminated film and manufacture thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4388139A (en) * 1980-07-14 1983-06-14 Fuller David L Thermosensing article and method of manufacture
US4332759A (en) * 1980-07-15 1982-06-01 Celanese Corporation Process for extruding liquid crystal polymer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072210A1 (en) * 1981-08-06 1983-02-16 Celanese Corporation Multiaxially oriented high performance laminates comprising uniaxially oriented sheets of thermotropic liquid crystal polymers
EP0133552A1 (en) * 1983-08-13 1985-02-27 BASF Aktiengesellschaft Process for producing a sheet semi-product
EP0201029A2 (en) * 1985-05-08 1986-11-12 Bayer Ag Manufacturing method of articles and sheets of thermotropic polymers
JPS6255130A (en) * 1985-09-05 1987-03-10 三井東圧化学株式会社 Laminated molded shape
JPS6295213A (en) * 1985-10-23 1987-05-01 Asahi Chem Ind Co Ltd Laminated film and manufacture thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JAPANESE PATENTS GAZETTE, section Ch, week 8715, 27th May 1987, class A, page 26, no. 87 106378/15, Derwent Publications Ltd, London, GB; & JP-A-62 055 130 (MITSUI TOATSU) 10-03-1987 *
JAPANESE PATENTS GAZETTE, section Ch, week 8723, 22nd July 1987, Class A, page 8, no. 87-160412/23, Derwent Publications, London, GB; & JP-A-62 095 213 (ASAHI CHEMICAL) 01-05-1987 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0568083A1 (en) * 1992-04-30 1993-11-03 Mazda Motor Corporation Method for molding a liquid crystal resin sheet and molding apparatus thereof
US5395470A (en) * 1992-04-30 1995-03-07 Mazda Motor Corporation Method for molding a liquid crystal resin sheet and molding apparatus thereof

Also Published As

Publication number Publication date
US4902369A (en) 1990-02-20
EP0310352A3 (en) 1989-07-19
BG50083A1 (en) 1992-05-15

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